This study comprehensively investigated mercury (Hg) contents of various environmental compartments in a typical antimony-coal mining area with intensive industrial activities over the past 120 years to analyze Hg environmental behaviors and evaluate Hg risks. The total mercury (THg) contents in river water, sediments, soils, PM₁₀, dust falls, vegetables and corns were 1.16 ± 0.63 µg/L, 2.01 ± 1.64 mg/kg, 1.87 ± 3.88 mg/kg, 7.87 ± 18.68 ng/m³, 13.01 ± 14.53 mg/kg, 0.30 ± 0.34 mg/kg and 3.11 ± 0.51 µg/kg, respectively. The δ²⁰²Hg values in soils and dust falls were − 1.58 ∼ 0.12‰ and 0.25 ∼ 0.30‰, respectively. Environmental samples affected by industrial activities in the Xikuangshan (XKS) presented higher THg and δ²⁰²Hg values. Binary mixing model proved that atmospheric deposition with considerable Hg deposition flux (0.44 ∼ 6.40, 3.12 ± 2.20 mg/m²/y) in the XKS significantly contributed to Hg accumulations on surface soils. Compared with soils, sediments with more frequent paths and higher burst probabilities presented higher dynamic Hg risks. Children were faced higher health risk of multiple Hg exposure than adults. Furthermore, the health risk of THg by consuming leaf vegetables deserved more attention. These findings provided scientific basis for managing Hg contamination.